EP0005963B1

EP0005963B1 - Method of plasma depositing a glass, a glass or silica optical fibre preform produced by this method, and method of making a silica optical fibre from this preform

Info

Publication number: EP0005963B1
Application number: EP79300931A
Authority: EP
Inventors: Henley Frank Sterling; Miles Patrick Drake
Original assignee: International Standard Electric Corp
Current assignee: International Standard Electric Corp
Priority date: 1978-05-30
Filing date: 1979-05-24
Publication date: 1983-04-06
Also published as: FR2427310B1; FR2427310A1; JPS54156828A; ES481010A1; GB1603949A; AU526306B2; BE876629A; AR222334A1; US4349373A; EP0005963A1; DE2965131D1; AU4732079A

Description

This invention relates to inductively sustained low pressure radio frequency plasma reactions, and in particular to a plasma process for the deposition of glassy material on to a solid surface, e.g. in the manufacture of optical fibre _.preforms.
The inductively sustained radio frequency plasma has been known for many years. The essential feature of the inductively sustained discharge is that the power is introduced into the gas phase by inductive coupling and hence the conductor paths in the gas form closed paths within the container. This provides a hot intense plasma and has the advantage that no internal electrodes are required nor are there the problems with large potential drops, as can occur with capacitive coupling, at the walls of the containing vessel.
The term 'radio frequency' as used herein is understood to include microwave frequencies. An inductively sustained discharge, or H-discharge, is produced by the magnetic field (H) of the exciting coil, unlike a capacitively sustained discharge or E-discharge which is relatively diffuse and is produced by electrostatic fields. A conventional E-discharge is achieved at relatively low pressure and low power. An H-discharge however occurs at intermediate pressures e.g. between about 13 and about 6600 Pascals (0.1 to 50 Torr) and requires medium to high input power points maintenance. The various forms of plasma are discussed in greater detail by G. I. Babat J. Inst. Elec. Eng. 94 27-37 (June 1947). It has been found that the H & E discharges become indistinguishable as the wavelength of the exciting radiation becomes comparable with the dimension of the discharge.
At low pressures the discharge tends to be most intense at the walls of a containing tube. At higher pressure about 66500 Pascals (500 Torr) the discharge becomes more restricted to the centre of the tube.
A typical plasma deposition process is described in our U.K. patent specification No. 1,104,935 which describes processes for depositing such materials as silica, silicon nitride and silicon carbide on a cold or heated solid surface. In this arrangement the discharge is primarily capacitively coupled to the radio-frequency power generator and thus, whilst the discharge provides the necessary energy for a chemical reaction to proceed, the energy density is relatively low and provides very little heating of a non-conductive substrate on which the reaction products are to be deposited.
In an attempt to provide sufficiently rapid deposition rates for optical fibre preform manufacture a combination of plasma deposition and thermal deposition has been investigated. Such a technique is described in U.K. patent Specification No. 1,519,994. In this arrangement a plasma is maintained at low pressure inside a silica tube whilst heat is applied to the outside of the tube to enhance deposition of the reaction products and to fuse the reaction product on to the inner surface of the tube.
In order to reduce the risk of tube collapse, glass discharge processes at atmospheric pressure or higher pressures have been investigated. Such processes are described in French patent specification No. 2,360,522 and use frequencies in the range 1 KHz-100 MHz.
The present invention provides a process for . depositing at a pressure below the atmospheric pressure silica in glassy form at rapid deposition rates which can be operated in the whole range of radio frequencies including microwave frequencies and provides the necessary heating of the substrate tube from its inner instead of its outer surface.
According to the present invention there is provided a method of depositing undoped and/or doped silica in glassy form on the inner surface of a silica tube, including supplying to the tube vapours containing at least the elements of silica at a pressure between 13 and 2660 Pascal (0.1 and 20 Torr), striking and maintaining within the tube an inductively sustained radio frequency (RF) plasma the largest dimension of which is significantly less than the free space wavelength of the radio-frequency employed to sustain the plasma so as to cause silica deposition on the inner surface of the tube, and traversing the discharge along the tube so as to provide a uniform silica coating, characterised in that the energy input to the plasma discharge is sufficient to heat the inner surface of the solica tube to a temperature sufficient for the deposition of glassy silica without fusion of the tube and loss of tube geometry.
Embodiments of the invention will now be described with reference to the accompanying drawings in which:

Fig. 1 is a schematic diagram of an inductive plasma deposition arrangement;
Fig. 2 indicates the plasma configuration obtained in the arrangement of Fig. 1;
Fig. 3 shows an alternative deposition arrangement;
Fig. 4 shows a further type of. deposition arrangement; and
Fig. 5 shows an alternative arrangement employing a radio-frequency concentrator.

Referring to Fig. 1, there is shown an arrangement for the deposition of a solid material on the inner surface of an insulating, e.g. glass or silica, tube 11. The tube 11 is evacuated via a pump 12 coupled to a pressure gauge 13 and is supplied with reactant gases via valves 14. Thus, for example, if silica is to be deposited on the inner surface of a silica tube in the manufacture of optical fibre preforms, the reactant gases may be silicon tetrachloride (SiCI₄) and oxygen together with an inert carrier gas such as argon.
Radio frequency power is supplied to the tube 11 via a voil 15 coupled via a flexible RF feeder 10 and a loading coil 16 to a generator 17.
An earthed electrode 18 is provided at one end of the tube downstream from the coil 15 as it has been found that this aids the initiation of an inductive plasma within the coil 15 and causes any capacitive discharge to be confined downstream of the coil. It is essential that the lower potential or earthed end of the coil 15 faces the incoming gas flow to the system.
It has been found for example that, using an approximately 5 cm (2 inches) silica tube, the minimum power required to strike and sustain an inductive plasma at a frequence of 3 MHz is from 4 to 6 kW. However as it is preferable to have an ample power reserve a 24 kW generator may be employed. Matching of the generator to the plasma is provided by adjustment of the loading coil 16 and, as will be apparent to those skilled in the art, by the particular design of the coil 1 5 surrounding the tube. In this respect it should be noted that, when an inductive plasma on H. discharge is struck within the tube, the parallel inductance effect of the plasma on the coil 15 reduces the effective inductance of that coil causing the generator frequency to rise. This is opposite to the effect observed with capacitors or E-discharge where striking of the plasma causes the generator frequency to fall.
Referring now to figure 2, the plasma 31 is struck with the tube 11 evacuated to the desired pressure in the range about 13 to about 6600 Pascals (0:1 to 50 Torr) by increasing the generator power until electrical breakdown of the gas occurs. The inductive plasma may then be sustained at a somewhat lower power level. As shown in Fig. 3 the plasma 31 is displaced from the centre of the coil 15 by the gas flow along the direction of the arrow A forming a broad front 32 against the gas flow and having an extended tail portion 33. Solid material 34, e.g. silica, is deposited on the tube from the plasma forming a ring of material adjacent the front 32 of the plasma 31. Thus, by moving the coil 15 along the tube 11, or by moving the tube within the coil, a contiguous layer of material may be deposited along the inner surface of the tube. The generator power may be so controlled that, whilst maintaining the inductive plasma, the solid material 34 is deposited directly in a glassy condition without fusion of the silica tube 11 and without the need to sinter the deposited material. Relative movement of the coil 15 and the tube 11 prevent overheating and subsequent collapse of any one portion of the tube 11.
The technique is particularly advantageous for the manufacture of silica optical fibre preforms by the coated tube method. Thus various layers of doped and/or undoped silica may be deposited on the inner surface of a silica tube without fusion of the tube and subsequent loss of tube geometry. The coated tube may then be collapsed into a preform tube and drawn into optical fibre in the normal way.
In a typical deposition process using the apparatus of Fig. 1, silica in glassy form may be deposited over a 40 cm length of 20 mm diameter silica tube by admitting 200 cc/min oxygen bubbled through silicon tetrachloride liquid at 20°C and admitting an additional 200 cc/min of oxygen into the tube at a pressure of about 955 Pascals (7.0 Torr). Conveniently the work coil 15 may comprise a two layer coil, 5 turns on the first layer wound on a 3 cm former, and 3 turns on the second layer. The turns may be insulated with glass sleeving and the two layers separated e.g. with a silica tube. The inductive plasma may be maintained at 2.9 MHz at a power level sufficient to heat the tube to about 1000°C, the coil being reciprocated along the tube at a rate of 5 secs per pass. This provides a deposition rate of glassy silica on the tube of 16 g/hour. Dopants commonly employed in the production of optical fibres may of course be included in the plasma to vary the refractive index of the deposited material.
It has been found that, using the arrangement of Figs. 1 and 2, by adjusting the generator output and, if necessary, by local heating of the deposition tube an inductive plasma may be struck and conveniently confined to the region of the work coil at pressure up to about 2660 Pascals (20 Torr). At pressures up to about 6600 Pascals (50 Torr) the tube diameter should be increased, i.e. above 20 mm, to improve matching and facilitate maintenance of the plasma.
Fig. 3 shows an inductive plasma deposition arrangement for the plasma deposition of material by a tube-in-tube process in which a tube 41 on which material is to be deposited rests or is supported in an outer tube 42. This technique, when applied to the coating of a silica tube e.g. for optical fibre production, has the advantage that the tube 41 may be maintained at a temperature approaching its softening point without the risk of collapse due to the relatively low pressure of the plasma. It is found with this arrangement that the plasma confines itself to the inside of the tube 41 and that deposition takes place therefore only on the inside of this tube. By this means the temperature of the inner tube may be raised to 1300°C without risk of distortion.
Fig. 4 shows a modification of the arrangement of Fig. 3 in which provision is made for the treatment of a plurality of tubes 51 by a semi- continuous tube-in-tube process. The tubes 51 to be treated are stacked in a vacuum tight storage chamber 52 communicating with a tube 53 in which the tubes 51 are to be treated. Reactant gases are supplied to the system via an inlet 54 into the storage chamber 52. To effect inductive plasma deposition, the bottom tube 51 of the stack is pushed e.g. by a piston (not shown) into the tube 53 and plasma coated with the desired material, e.g. silica or doped silica, as previously described. When coating has been completed the next tube 51 of the stick is pushed into the tube 51 ejecting the previously coated tube 51 into a further storage chamber 55. The process is then continued until all the tubes 51 have been treated.
In the arrangement of Fig. 5, a current concentrator or RF transformer 61 is employed to localise and intensify the H-discharge. Hitherto it has not been possible to apply such a current concentrator, to plasma systems operating at atmospheric pressures.
Such a transformer can be employed to effectively isolate the high voltage associated with the primary coil 15 from the plasma region and also provide a step down-high current path which can be used to stabilise and concentrate the plasma to the required deposition zone. Typically the concentrator, which should be water cooled, comprises a conductive, e.g. copper, hollow cylinder provided with a longitudinal slot 62 and closed at one end by a plate 63 provided with a keyhole slot 64 communicating with the slot 62. The discharge tube is placed in the keyhole slot 64 around which intense RF current is induced by the surrounding work coil (not shown). As the con- centractor is isolated from the generator it may be earthed thus eliminating any stray capacitive discharges or maintained at any desired potential. Other forms of concentrator known to those skilled in the art may of course be used.
The following examples illustrate the invention:-

Example 1

A silica deposition tube of 21 mm internal diameter was mounted in a vacuum pumped flow system of the type shown in Fig. 1. The tube was pumped by a rotary vacuum pump through a liquid nitrogen cold trap, the tubing between pump and deposition tube being designed to give a high flow conductance.
A work coil was constructed from two layers of approximately 6.5 mm (¼") copper tube wound with five turns on the inside layer and three turns on the outside. The coil was insulated with glass fibre sleeving and isolation between the two layers was achieved by means of a silica tube.
The coil was placed over the silica tube and connected by means of flexible water cooled leads to the tank circuit of a 35 kW RF generator. Provision was made for reciprocation of the coil along 50 cm of the silica tube.
As stray capacitator effects resulting from discharge from high RF voltage parts of the coil were found to promote sooty deposition incorporated in the glassy deposit, the coil was arranged with the earthed end on the inside of the coil and facing the incoming gas stream. Stray discharges were then more or less confined to the down-stream end where no unreacted silicon tetrachloride existed.
The silica tube was pumped down to less than 0.01 Torr. When the pump operating 200 cc/min of O2 was admitted causing the pressure in the tube to rise to about 260 Pascals (2 Torr). The voltage to the oscillating valve was then increased briefly to 3 kv when an intense white plasma appeared within the tube confined to the coil region.
The frequency before the plasma appeared was 4.54 MHz and on appearance of the plasma this increased to 4.62 MHz as the inductance of the coil was reduced by the inductive plasma.
The voltage to the valve was then adjusted until the tube temperature rose to 1100°C.
Silicon tefrachloride was then admitted by bubbling oxygen through the liquid at 22°C at a rate of 300 cc/min causing the pressure to rise to about 400 Pascals (3 Torr). After one hour the tube was removed and it was found by weighing that 16 g of silica had been deposited in a glassy form.

Example 11

A coil and concentrator of the type shown in Fig. 5 were used. A ten turn coil was wound as before (Ex. 1) on an internal diameter of 55 mm. A water cooled copper concentrator was inserted and earthing provided to it by means of a switch. Note that in some applications the concentrator may be maintained at any chosen RF potential with respect to earth.
The coil and concentrator were connected to the tank circuit of the generator. The voltage on the valve was increased as before until an H-discharge appeared in the region of concentrator field. The voltage was then adjusted to give a tube temperature of 1200°C. The concentrator was then earthed and all trace of stray capacitive discharges disappeared.
Silicon tetrachloride and germanium tetrachloride were admitted in the usual way to cause a layer of doped Si0_2/Ge0₂ to be deposited on the tube.

Claims

1. A method of depositing undoped and/or doped silica in glassy form on the inner surface of a silica tube, including supplying to the tube vapours containing at least the elements of silica at a pressure between about 13 and about 2660 pascal (0.1 and 20 Torr), striking and maintaining within the tube an inductively sustained radio frequency (RF) plasma the largest dimension of which is significantly less than the free space wavelength of the radio frequency employed to sustain the plasma so as to cause silica deposition on the inner surface of the tube, and traversing the discharge along the tube so as to provide a uniform silica coating, characterised in that the energy input to the plasma discharge is sufficient to heat the inner surface of the silica tube to a temperature sufficient for the deposition of glassy silica without fusion of the tube and loss of tube geometry.

2. A method as claimed in claim 1, characterised in that the plasma is provided by oxygen and silicon tetrachloride vapour.

3. A method as claimed in claim 1 or 2, characterised in that the silica tube is supported in an outer vacuum tight silica tube.

4. A method as claimed in any one of claims 1 to 3, characterised in that said plasma includes one or more dopant elements for varying the refractive index of the deposited material.

5. A method as claimed in any one of claims 1 to 4, characterised in that the plasma is localised by means of an RF step down transformer or concentrator.

6. A method as claimed in claim 5, characterised in that the concentrator is earthed or is maintained at a potential with respect to earth.

7. A silica optical fibre preform tube produced by collapsing a coated silica tube produced by a process as claimed in any one of the preceding claims.

8. A silica optical fibre drawn from a preform tube as claimed in claim 7.